Molecular Dynamics Study of Morphology of Doped PEDOT: From Solution to Dry Phase

Franco-González, Juan Felipe; Zozoulenko, Igor

doi:10.1021/acs.jpcb.7b01510

Cited by 70 publications

(166 citation statements)

References 82 publications

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“…Additionally, a narrow and monodispersed molecular weight distribution is expected, which justifies the use of all of PEDOT chains with the same chain length in our simulation box. Finally, we note that that for the case of PEDOT:TOS the calculated morphology was shown to be rather insensitive to the chain length N …”

Section: Methodsmentioning

confidence: 85%

“…Notably theoretical modelling, that is an essential and standard tool in many fields of material science, is to a large extend missing in conducting polymer research where the interpretation of experiments seldom relies on theoretical calculations. Recently, some of the present authors reported molecular dynamics (MD) simulations of morphology and crystallization of PEDOT with tosylate (Tos – ) as the doping anion . At the same time, the theoretical understanding of the effect of different anions on electronic, structural, and morphological properties of the system at hand remains elusive and practically unexplored.…”

Section: Introductionmentioning

confidence: 99%

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Charge transport and structure in semimetallic polymers

Rudd

Franco-González

Singh

et al. 2017

J Polym Sci B Polym Phys

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Owing to changes in their chemistry and structure, polymers can be fabricated to demonstrate vastly different electrical conductivities over many orders of magnitude. At the high end of conductivity is the class of conducting polymers, which are ideal candidates for many applications in low‐cost electronics. Here, we report the influence of the nature of the doping anion at high doping levels within the semi‐metallic conducting polymer poly(3,4‐ethylenedioxythiophene) (PEDOT) on its electronic transport properties. Hall effect measurements on a variety of PEDOT samples show that the choice of doping anion can lead to an order of magnitude enhancement in the charge carrier mobility > 3 cm2/Vs at conductivities approaching 3000 S/cm under ambient conditions. Grazing Incidence Wide Angle X‐ray Scattering, Density Functional Theory calculations, and Molecular Dynamics simulations indicate that the chosen doping anion modifies the way PEDOT chains stack together. This link between structure and specific anion doping at high doping levels has ramifications for the fabrication of conducting polymer‐based devices. © 2017 The Authors. Journal of Polymer Science Part B: Polymer Physics Published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018, 56, 97–104

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Section: Methodsmentioning

confidence: 85%

Section: Introductionmentioning

confidence: 99%

Charge transport and structure in semimetallic polymers

Rudd

Franco-González

Singh

et al. 2017

J Polym Sci B Polym Phys

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“…The different PEDOT:Tos morphologies studied in this work were generated by molecular dynamics simulations (MD) following the methodology developed in previous works [42][43][44]. The initial systems are mixtures of positively charged PEDOT oligomers, Tosylate anions and water molecules; the system has a neutral charge when the total positive charge carried by the PEDOT oligomers exactly compensate the Tosylate anionic charge.…”

Section: A From Morphology To Resistive Networkmentioning

confidence: 99%

“…The initial water concentration is set to W = 82% w/w, and the crystallization of PEDOT oligomers and evolution of the morphology of the system is investigated by consequently removing a part of the water molecules and iteratively equilibrating the system at ambient temperature from the initial highly hydrated phase to a dry phase until no water remains in the same way at this has been done in Ref. [42] (see the Supporting Information for details [45]). …”

Section: A From Morphology To Resistive Networkmentioning

confidence: 99%

Understanding morphology-mobility dependence in PEDOT:Tos

Rolland

Franco-González

Volpi

et al. 2018

Phys. Rev. Materials

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103

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The potential of conjugated polymers to compete with inorganic materials in the field of semiconductor is conditional on fine-tuning of the charge carriers mobility. The latter is closely related to the material morphology, and various studies have shown that the bottleneck for charge transport is the connectivity between well-ordered crystallites, with a high degree of π -π stacking, dispersed into a disordered matrix. However, at this time there is a lack of theoretical descriptions accounting for this link between morphology and mobility, hindering the development of systematic material designs. Here we propose a computational model to predict charge carriers mobility in conducting polymer PEDOT depending on the physicochemical properties of the system. We start by calculating the morphology using molecular dynamics simulations. Based on the calculated morphology we perform quantum mechanical calculation of the transfer integrals between states in polymer chains and calculate corresponding hopping rates using the Miller-Abrahams formalism. We then construct a transport resistive network, calculate the mobility using a mean-field approach, and analyze the calculated mobility in terms of transfer integrals distributions and percolation thresholds. Our results provide theoretical support for the recent study [Noriega et al., Nat. Mater. 12, 1038] explaining why the mobility in polymers rapidly increases as the chain length is increased and then saturates for sufficiently long chains. Our study also provides the answer to the long-standing question whether the enhancement of the crystallinity is the key to designing high-mobility polymers. We demonstrate, that it is the effective π -π stacking, not the long-range order that is essential for the material design for the enhanced electrical performance. This generic model can compare the mobility of a polymer thin film with different solvent contents, solvent additives, dopant species or polymer characteristics, providing a general framework to design new high mobility conjugated polymer materials.

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“…[6,18] (The electronic structure and optical transitions of polaronic states in polymer chains are discussed in refs. [18] and [19]).The experimental studies of the morphology [11,[20][21][22][23] as well as the molecular dynamics simulations [24] demonstrate that PEDOT films are composed of small crystallites consisting of 3-10 π-π stacked PEDOT chains surrounded by less ordered regions as well as counterions. A schematic energy diagram of a representative crystallite showing an onset of a formation of the bipolaronic band is depicted in Figure 1c.…”

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confidence: 99%

Understanding the Impact of Film Disorder and Local Surface Potential in Ultraviolet Photoelectron Spectroscopy of PEDOT

Muñoz

Crispin

Fahlman

et al. 2017

Macromol. Rapid Commun.

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The spectra of conducting polymers obtained using ultraviolet photoelectron spectroscopy (UPS) exhibit a typical broadening of the tail σ ≈ 1 eV, which by an order of magnitude exceeds a commonly accepted value of the broadening of the tail of the density of states σ ≈ 0.1 eV obtained using transport measurements. In this work, an origin of this anomalous broadening of the tail of the UPS spectra in a doped conducting polymer, PEDOT (poly(3,4-ethylenedioxythiophene)), is discussed. Based on the semiempirical approach and using a realistic morphological model, the density of valence states in PEDOT doped with molecular counterions is computed. It is shown that due to a disordered character of the material with randomly distributed counterions, the localized charge carriers in PEDOT crystallites experience spatially varying electrostatic potential. This leads to spatially varying local vacuum levels and binding energies. Taking this variation into account the UPS spectrum is obtained with the broadening of the tail comparable to the experimentally observed one. The results imply that the observed broadening of the tail of the UPS spectra in PEDOT provides information about a disordered spatially varying potential in the material rather than the broadening of the DOS itself.

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Molecular Dynamics Study of Morphology of Doped PEDOT: From Solution to Dry Phase

Cited by 70 publications

References 82 publications

Charge transport and structure in semimetallic polymers

Charge transport and structure in semimetallic polymers

Understanding morphology-mobility dependence in PEDOT:Tos

Understanding the Impact of Film Disorder and Local Surface Potential in Ultraviolet Photoelectron Spectroscopy of PEDOT

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